2

CHAPTER 2

FUELS AND COMBUSTION

"Probablyfor onlya linmited number
ofyears to come, the largest
ffossil fuels". portion ofthe world'spower
will comefrom the combustion

1 INTRODUCTION
Fuel is a combustible substance, containing
carbon as main constituent,
amount of heat, which can be used economically which on proper burning gives
for domestic and industrial purposes. large
kerosene, petrol, diesel, producer gas, oil gas, etc. Wood, charcoal, coal,
are some of the fuels.
During the process of combustion of a fuel
(like coal), the atoms of carbon, hydrogen,
with the simultaneous liberation of heat at a etc. combine with
elections" in these atoms,
rapid rate. This energy is liberated due to the "rearrangement oxygen
resulting in the formation of new of valency
compounds have less energy (or heat compounds (like cO2 H,0, etc.). These new
content) in them and, therefore, the energy
combustion process is the difference
in the energy of the reactants (C, (or heat) released during the
formed. H, and O, etc. of fuel) and that ofthe proucts
FUEL
PRODUCTS HEAT
More
heat energy content Lesser heat energy content
The primary or main source of fuels are coals
and petroleum oils, the amounts of which are dwindling
These are stored fuels available in earth's crust day-by-day.
and are, generally, called 'fossil fuels'.
2 CLASSIFICATION OF FUELS
The fossil fuels have been classified according to their:occurrence
aggregation. According to the first classification, we (and preparation), and (2) the state of
have-fr)natural or primary fuels, which are found in nature
as such, e.g., wood, peat, coal, petroleum, natural gas, etc. ; (b) artificial
or
prepared form the primary fuels. For example, charcoal, coke, kerosene oil, secondary fuels are those which are
diesel oil, petrol, coal gas, oil gas,
producer gas, blast furnace gas, etc.

CHIMICAL FUELS

PRIMARY OR
SECONDARY OR
NATURAL DERIVED
State of State of
aggregation aggregation

Solid Liquid Gaseous Solid Liquid Gaseous

Wood Crude oil Natural gas Coke Tar Coal gas
Peat Charcoal Kerosene Water gas
Lignite Petroleum Diesel Oil gas
Coal coke Petrol Biogas
Dung Coal Fuel oil Blast furmace
briquette Synthetic gas
gasolien Coke oven gas
L.P.G.
(55)
 ENGINEERING CHEMISTRY
56
state of aggregation like: (a) solid fuels; (b) liquid fuels,
The second classification is based upon their
fuels is summarized as on page.
and (c) gaseous fuels. The classification of
powdered coal in fuel oil (or any other liquid fuel), generally,
in the ratio
Note: Colloidal fuel is.a suspension finely
of colloidal fuel in order to avoid
of 3:2 by weight. Usually, some stabilizing agent is added during the preparation calorific values and it is easy to
fuel. In general. Such fuels possess higher
the separation of coal from the liquid
in industrial furnaces for cement
handle them compared with powdered coal and these such fuels find applications
manufacture, brick firing, ceramic firing, metal processing, etc.

3 CALORIFIC VALUE
when a unit mass (or volume) of
Calorific value of a fuel is "the total quantity of heat liberated,
the fuel is burnt completely"
of water through
is the amount of heat required to raise
the temperature of onie grami
Units of heat: (1) 'Calorie'
one degree Centigrade (15-16°C).
is the unit of metric
2)"Kilocalorie" (or "Kilogram Centigrade units") is equal to 1,000 calories. This
one kilogram of water through
raise the temperature of
system and may be defined as 'the quantity of heat required to
onedegree Centigrade. Thus
=
1 kcal 1,000 cal
to raise the tenuperature
(B.Th.U.) is defined as "the quantity of heat required
(3) "British Thermal unit" system unit.
pne degree Fahrenheit (60-61°E). This is the English
of one pound of water through
1 B.Th.U. = 252 cal = 0.252 kcal

tkcal=3.968 B.Th.U.
required to raise the temperature of pound of
Or 1

"the quantity of heat

(4) "Centigrade heat unit'(C. H. U.) is
water through one degree Centigrade." Thus
kcal = 3.968 B.Th.U. = 2.2 C.H.U.
1
the calorific value
fuels contain some hydrogen and when
Higher or gross calorific value Usually, all
:

determined experimentally, the hydrogen is converted into steam. If the

fuel is
of hydrogen-containingare condensed 60°F), the latent heat of condensation
to the room temperature (15°C or
products of combustion calorific value". Solgross
steam also gets included in the measured heat, which is then called "higher or gross
of produced, when unit mass /volume of the fuel has been
or higher calorific value (HCV) is "the total amount of heat or 60°F
connpletely and the products of combustton have been cooled to room temperature (.e., 15"T
burnt
fuel, the water vapour and moisture, etc., are not
Lower or net calorific value: In actual use of any So,
combustion gases. Hence, a lesser amount of heat is available.
condensed and escape as such along-with hot completely_
net produced, when unit mass/volume of the fuel burnt
is
net or lower calorific value (LCV) is the heat
Alternatively, net or lower calorific value (LCV)
and the products are permitted to escape".
= HCVLatent heat of water vapour formed
=
HCV- Mass of hydrogen x 9 x Latent heat of steam
by mass of vater. The latent heat of steam is 587 kcal/kg or
because 1 part by mass of hydrogen produces 9 parts
1,060 B.Th.U./lb of water vapour formed at room
temperature (i.e., 15°C).
calorielgram (callg) or kilocal-
Units of calorific value: The calorific value is, generally, expressed in
of solid or liquid fuel. In case of gaseous fuels,
orielkg (kcal/kg) or British thermal unit/lb (B.Th.U/lb) case
in
metre ( kcal/m) or B.Th.U/cubic feet (B.Th.U./ft').
the units used are kilocalorielcubic
1 kcal/kg=1.8 x B.Th.U./1b
1 kcal/m =0.1077 x B.Th.U./ft° .(1)
= 9.3
.B.Th.U./fr kcal/m

CHARACTERISTICS OF A GOOD FUEL

High calorific value : A fuel should possess high calorific value, since the amount of hent liberaled
and temperature attaned thereby depends upon the calorific value of fuel.
 FUELS AND COMBUSTION
57
Moderate ignition temperature: Ignition temperature is the lowest temtperature
he pre-heated so that it starts burning smoothly.
Low ignition temperature
towhich the fuel ust
of fuel, since it can cause fire hazards. On the is dangerous for storage and transport
igniting) other hand, high ignition temperature causes dificulty
lor the fuel, but the fuel is safe during in kindling
"moderate" ignibiön temperature.
storage, handling and transport. Hence, an ideal fuel should have
Mow
money,
moisture content: The moisture content of the fuel reduces the heating
value and involves
a loss of because it is paid for at the same in
rate as the fuel. Hence, fuel should have low moisture content.
Low non-combustible matter
oenerally, in the form of ash or clinker. content: After combustion, the non-combustible matter remains,
The non-combustible matter also
additional cost of storage, handling reduces the heating value, besides
and disposal of the waste
bustible matter in fuel means a heat loss of products produced. Each per cent of non-com-
about 1.5%. Hence, a fuel should have low content of non-combustible
matter.
YModerate velocity of combustion: If the rate of combustion
temperature may not be possible, because is low, then the required high
a part of the heat liberated may
temperature. On the other hand, too high get radiated, instead of raising the
combustion rates are also not required.
Products of combustion should not be
harmful: Fuel, on burning, should not give out objection-
able and harmful gases. In other words, the
gaseous products of a combustion should not pollute the
atmosphere. CO SO2HS, PH3, etc., are some of
the harmful gases.
Low cost: A good fuel should be readily available in bulk at a cheap rate.
Easy to transport:Fuel must be easy to handle, store and transport at a low cost. Solid
fuels can easily be transported from one place to and liquid
another. On the other hand, transportation of gaseous fuels
is costly and can even cause fire hazards.
Combustion should be easily controllable, i.e., combustion of the fuel should be easy to start or stop,
twhen required.
ey Should no undergo spontaneous combustion:Spontaneous ignition can cause fire hazards.
G Storage cost in bulk should be low.
2y Should burn in air with efficiency, without much smoke.
(13) In case of solid fuel, the size should be uniform so that combustion is regular.

5 cOMPARISON BETWEEN SOLID, LIQUID AND GASEOus FUELS

(A) Solid Fuels : Advantages:(1) Theyare.casytotransport.(2)They areconvenient tostore,without
any risk of spontaneous explosion. (3) Their cost ofprodiuctionis lou. (4) They possessmoderateigntion Lomperatures.
Disadvantages: (1) Their ash content is high. (2) Their large proportion of heat is wasted during
combustion. In other words, their thermal efficiency is low. (3) They burn with clinker formation. (4) They
combustion operations cannot be controlled easily. (5) Their cost of handling is high. (6) Theircalorificvalue
is lower as compared to that of liquid fuels. (7) They require large excess of air for complete combustion. (S) They
cannot be used as internal combustion engine fuels.

(B)Liquid Fuels: Advantages (1) They possess highercalorificvalue per unit mass-than-solid fuels.
(2) They burn without forming dust,ash,clinkers,etc. (3) Their firing is easier and also fire can be extinguished
easily by stopping the liquid fuel supply. (4) They areensytotransport through pipes. (5) They can be stored
indefinitely, without any loss. (6) The flame produced by burning liquid fuels can easilybe controled by
adjusting the liquid fuelsupply. (7) Liquid fuels are, generally, handled by pipes and one man can easily
regulatea large number of furnaces simultaneously. (8) They are clean in use and economic in labour. (9) Los
of heat to chimney is very loto, due to greater cleaniiness. (10) They require less excess ofair for complete
combustion. (11) They require lessfurnace space for combustion. (12) There is no wear and tear of grate bars
and cleaning of fires, etc., unlike solid fuels. (13) They can be used as internal combustion fuels
 NGINEERING
CHEMIS
58
relativelymuch higher as compared hazaa to salt fuelsg
cost of liquid fuel is There is a greater risk of
fire Costl
Disadvantages The for storing liquid fuelsu
odour.yG}For efficient
Particua
special storage tanks are required fuel. They givebad
case of a highly inflammable and
volatile liquid
apparatus are required. bthoking of spravers
sprayersgof liquid h
(duringliquid
constructed burners and spraying
fuels, specially
firing.
fuel combustion) is a drawback of oil through pipelines to the
Advantages <YThey can be conveyed ensily th actual
place
(C) Gaseous Fuels: They can be light
ghted at
manual labour in transportation.2 mon
notice
of need, thereby eliminating teuperatures. 4They can be be
content and hence, help us in having igher pre-leated
They have high heat combustion can readil by
heat of hot waste gases, thereby affording economy in heat. (heir temperature, (
be ntrollei
the flame, etc
tor changes in demand like oxidizing or
reducing atmosphere, length of etc. (7 heybum
there is no labour involed in ash handling,
Twithout any soot for smoke) and are ashless, so even.
special burners. (9) They can be produced by using the
Clenn in useal8) They do ngt require any currents. (J}They burn P0Test
loss, due to convection
quantity of coal, etc. (10 They burn without heat
excess of air supply. (12yThey are free from solid and
liquid impurities. Hence, they do not affect iethght
produced, when used as a metallurgical fuel.Y3) Complete combustjøn without pollution ality
of metal calorific values. (5) They can also be used inta
as
due to uniform mixing of air and fuel. (14) They have high
combustion engine fuels.
are highly inflammabie SO
Disadvantages (Very large storage tanks are needed for them.(They
chances of fire hazards are high in their use.(3YThey are
more costly as compared to solid and liquid fuele

BOMB CALORIMETER
This apparatus is used to find the calorific value of solid and liquid fuels.
Construction: A simple sketch of bomb calorimeter is shown in Fig. 1. It consists ofa strong
cylindrical stainless steel bomb in which the combustion of fuel is made to take place. The bomb
has a lid, which can be screwed to the body of bomb so as to make a perfect gas-tight seal. The lid
is provided with two stainless steel electrodes and an oxygen inlet valve. To one of the electrodes, a
small ring is attached. In this ring, a nickel or stainless steal crucible can be supported. The bomb is
placed in a copper calorimeter, which is surrounded by an air-jacket and zwater-jacket to prevent heat
losses due to radiation. The calorimeter is provided with an electrically operated stimer and
Beckmann's thermometer, which can read accurately temperature difference upto 1/100th ofa degree.

Beckmann's 6V
thermometer battery
Oxygen
valve
Electrically maudei
operated stirrer
Electrodes
to which a ring
is attached
Copper
calorimeter
Mg fuse wire
Stainless steel
Weighed pallet bomb Fig. 1. Bomb calorimeter.
of given fuel
sample
Stainless steel
crucible

Air jacket
Water jacket
FUELS AND COMBUSTION
59
Working: A known mass (about 0.5 1.0
to g) of the given fuel is taken in clean crucible. The
is then
suPported over the ring8. A fine crucible
dhe electrodes. The magnesium wire, touching the fuel sample, is then stretched across
bomb lid is tightly screwed
hamb is then lowered into copper and bomb filled with oxygen to 25 atmospheric pressure. Ihe
calorimeter, containing a known
initial temperature ot the water is noted. The mass of water. The stirrer is worked and
completed. The sample burns and electrodes are then connected to 6-volt battery and circuit
heat is liberated. Uniform
temperature attained is recorded. stirring of water is continued and the maximum
Calculation: Let x = mass in g of fuel
sample
calorimeter; t0 = water equivalent in g of calorimeter, taken incrucible; W = mass of water in the
temperature of water in calorimeter; stirrer, thermometer, bomb, etc. ; t = initial
calorific value in fuel in cal/g.
t final temperature of water in calorimeter;L =
higher
Heat liberated by burning of fuel = x L
andheat absorbed by water and apparatus, etc. = (W+tw)
But heat liberated by the fuel = Heat absorbed
(2-th)
by water, apparatus, etc.
L (W+w)(-t)
or HCV of fuel (L) (W+w) (t2-t)
cal/g (or kcal/kg) ..(2)
Note: The water equivalent ofthe calorimeter is determined
by burning a fuel of known calorific value and using
the above equation. The fuels used for this
purpose are benzoic acid (HCV = 6,325 kcal/kg) and naphthalene (EICV
=9,688 kcal/kg).
If H= percentage of hydrogen in fuel, then:
g
9H
Mass of H,O from 1 g of fuel = 0.09 H gs
Heat taken by water in forming steam
= 0.09 Hx 587 cal
Latent heat of steam = 587 cal/g)
LCV HCV Latent heat of water formed
-

(L-0.09Hx587) cal/g (or kcal/kg) 3)

Corrections: To get more accurate results, the following corrections are applied:
OMse wire connection: The heat liberated, as measured above, includes the heat given out
by ignifion of the fuse wire used.
iAcid correction: Fuels containing S and Nare oxidised, under high pressure and temper-
ature of ignition, to H,SO, and HNO, respectively.
S+2H+2O H,SO, +Heat
2N+2H+30 2HNO0,+Heat
Formation of these acids are exothermic reactions. So, the measured heat also includes the heat given
Out during the acid fornation. The amount of these acids is analysed from washings of bomb by
titration; while H,SO, alone is determined by precipitation as BaSO. The correction for 1 mg of
S is 2.25 cal; while for 1 mL of
N/10 HNO, formed is 1.43 cal.
Cooling correction: Time taken to cool the water in calorimeter from maximum temper
ature to room temperature is noted. From the rate of cooling (d1°/minute) and the actual time taken
for cooling (t minutes), the cooling correction of dt x is
t
added to the rise in temperature.
WF W)T2-11+ cooling correction) [Acid + fuse corrections]
-

.(4)
Mass of fuel (x)
 ENGINEERING
CHEMISTRY
62
space during the same
(Gi) the quantity ofwater (W kg) passing through the annular inte.
of time;
ii the steady rise in temperature (T2-T), and
water.
(1) the mass of water (steam) condensed (in kg) in the outlet
t; W= mass of cooli.
Calculations : Let V= volume of gas burms at STP in a certain time, ling
water used in time, t; T,= temperature of inlet water ;T2= temperature of outgoing water
=
m= mass of steam condensed in time t in a graduated cylinder; L higher calorific value of fuel
Then, heat absorbed by circulating water = WCT2-T

and heat produced by the combustion of fuel = VL

Assuming no heat loss, we get: VL=W(T2-T1)

or HCV (or GCV), L=

WT-T)
V 5)
Mass of H,O condensed per m' of gas = m/V kg
Latent heat of steam per m° of gas 11X587 kcal
V.

LCV (or NCV) ,mx567kcal/m ..(6)

THEORETICAL CALCULATION OF CALORIFIC VALUE OF A FUEL

The calorific value of fuel can be approximately computed by noting the amounts of the
constituents of the fuel. The higher calorific value of some of the chief combustible constituents of
fuel are tabulated below :

Table 1. Calorific values offuel constituents.

Constituent Hydrogen Carbon Sulphur
HCV (kcal/kg)_ 34,500 8,080 2,240
The oxygen, if present in the fuel, is assumed to be present in combined form vith hydrogen,
ie., in the form of fixed hydrogen [H,O]. So, the amount of hydrogen available
for combustion
= Total mass of hydrogen in fuel Fixed hydrogen
-

= Total mass of hydrogen in fuel (1/8) Mass of oxygen in the fuel

-

(:8 parts of oxygen combine with one part of

hydrogen to form H,0)
Dulong's formulafor calorific value from the chemical composition of
fuel is
HCV= 8,080 C+34,500 H-+2,240 S
|kcal/kg
100 8 ...(7)
where C, H, O, and S are the percentages of carbon, hydrogen, oxygen and sulphur in the fuel
respectively. In this formula, oxygen is assumed to be present in
combnation with hydrogen as
water, and
9 Hx
LCV=HCV-100 587 kcal/kg = [HCV -0.09
Hx 587] kcal/kg
This is based on the fact that 1 part of H by mass gives 9 parts of H,O, and latent heat of
steam is 587 kcal/kg.
 inlet gase
reversedand the gases. The flue gases are
then allo pa erbrick
Dr
heating gases is then
preheat inlet
the checker-work then
to toto
pass
serves preheat throus
the
thein
serves to heat it. This cycle goes on. The heating isactually inle
which thus to
second set of
checker bricks
reversed. Thus, this Carbonization chaually continue
Carbonization of a arge of .

again completely. coal

when the flow isvolatile matter ceases
the evolution of
hours. ram pushes the red hot.
kes
a
between 11 to 18
completed, a massive into a
carbonization is quenching"). In place of wet quenchinytruk
spray ('wet
nse, enchi
When
a water is more strong, dens
subsequently quenched by coke produced
advantages, because the a chamber and cooledphit nitized
quenching'" offers
method, the red hot coke 1s placed
in
circulated to
by passing
hoiPassin
non-reactive. In this gases are then to boil
nitrogen). The heated inert con ers,wher
gases from boilers (like quenching is cheaper, drier and containslesser
coke produced by 'dry
generate steam. The
coke.
than 'wet-quenched' as "coke oven one!'o
by-products: The gas coming out from the oven is known andismainh
Recovery of moisture, etc.
naphthalene, benzene, tar,
composed of ammonia, HS,
a tower in which liquor ammonia is
of tar: The gas is first passed through
() Recovery
to recover back amman
below, which is heated by steam coils
dust and tar get collected in a tank
The ammonia is used again.
are then passed through a tower in whic
(i) Recovery of ammonia : The gases from the chamber
is sprayed. Here ammonia goes into solution as NH,OH.
af
(i) Recovery ofnaphthalene: The gases are then passed through another tower in which water atvery
low temperature is sprayed. Here naphthalene gets condensed.
Civ) Recorvery of benzene: The gases are then sprayed with petroleum, when benzene and its homologu
are removed.
() Recovery of H2S: The. gases are then passed through a purifier, packed with moist Fe-O, He
HS is retained.
FeO3 +3 HS FeS + 3 H,O
After some time, when all FeS3 is changed into Fe2S3, the purifier
is exposed to atmosphere, when
FeO is regenerated.
FeS+ 4O2 2 FeO +3 SO
4FeO+Oz 2 Fe,O3
PETROLEUM
Petroleumor crude oil (petra = rock ; oleum =
crust It is composed mainly oil), is a dark greenish-brown, viscous found deep m
of various hydrocarbons (like straight-chain oil u
lenes olefinsand aromatics),together with paraffins, cycloparaffins orna htha-
small
andsulphur. The oil is, usually, found floating uponamounts
a layer
of organic compounds containing oxygeny nutrogen
composition of crude petroleum of brine and age
is :C=79.5to 87.1%; hasa layer of gas on top 0 1
H=11.5 to 14.8% ; S =0.1 05%
Classification of petroleum:
world in whtch 1s The chemical to 3.5% ;N+0U
1t found.There appears, however,nature of the crude petroleum varies witn tof the
Paraffinic-base type to be three principle t
crudeismainly varieties
a little of the naphthalenes composed of the
and aromatics. The saturated hydrocarbobons from CH4 to Cashcalled
waxes'. hydrocarbons
from CIRtlg to C35Hy2 are sernu
2Asphaltic-base type crude
paraffins and aromatic contains mainly
hydrocarbons. cycloparaffins amountof
or naphthalenes with sma
 FUELS AND COMBUSTION 13
CH

(Naphthalene) (Methyl naphthalene)

Mixed-base type crude contains both paraffinic and asphaltic hydrocarbons and are,
gen-
erally, rich in semi-solid waxes.
Origin of petroleum : According to modern theory, petroleum has resulted fronm the partialdeconmpositio
of marineaninmalsand vegetable organisms ofpre-historic forests. Changes in earth (like volcano's, etc.) had
burried
these materials underground, where they have been subjected to intense pressure and heat, during the ages
of time.The conversion of these materials into various hydrocarbons has been going on either under the
ntluence of radioactive substances (like uranium)or bythe bacterigl decomposition under anaerobic and
strongly reducing conditions and temperature under high-pressure.
Mining of petroleum done by drilling holes in the earth's crust and sinking pipes upto the oil-bearing
porous rocks. Oil, usually, gushes out itself due to hydrostatic pressure of natural gas. Alternatively, it may
be mechanically pumped up by using either lift pump or air-lift pump. The latter consists of truo co-axinl pipes,
lowered into the base of oil bed. Compressed air is forced through the outer pipe, whereby oil comes out through
the inner pipe (see Fig. 7). The oil is conveyed to refinery by a system of pipelines.

Copmressed air

Natural gas- Oil

Fig. 7. Mining of crude oil and use

of air-lift pump.

Natural gas

=: Brine

Refining of crude oil: The crude oil is separated into various useful fractions by fractional
distillation and finally converted into desired specific products. The process is called "refining of
crude oil" and the plants set up for the purpose, are called the oil refineries. The processs of refining
involves the following steps

step 1.Separation of water (Cottrell's process) The crude oil from the oil well is an
extremely stable emulsion ofotland salt water. The processoffreeing oil from water consistsin allowing
the crudeto flowbetween two highly charged electrodes.(The colloidal water-droplets coalesce to fornm
large drops, which separate out from the oil.

Step 2.Removal of harmful sulphurcompounds involves in treating oiluvithcopperoxideA

reaction occurs with sulphur compounds, which results in the formation of copper sulphide (a
solid), which is then removed by filtration.
 ENGINEERING CHEMISTRY
74
400°C in an iron retort
Step 3. Fractional distillation: The crude oil is then heated to about
whereby all volatile constituents, except the residue (alphalt or coke)
are evaporated. The hot
vapours are then passed up a "fractionating column", which is a tall cylindrical tower containing a
number of horizontal stainless steel trays at short distances (see Fig. 8). Each tray provided with
is
small chimney, covered with a loose cap. As the vapours go up, they become gradually cooler and
condenses
fractional condensation takes place at different heights of columnHigher boiling fraction
first; while the lower boiling fractions turn-by-turn.(Various principal fractionation products thus
obtained are given in Table 4.
/fable 4. Fractions by distillation of crude.
Approx. composition in
Name of Uses
Boiling range terms of hydrocarbon
fraction containing C atoms
1. Uncondensed Below 30°C C to C4 As domestic or industrial fuel under
gas. (such as ethane, propane, the name L.P.G. (liquefied petroleum
isobutane) gas).
2 Petroleum 30 70°C Cs-C7 As a solvent.
ether.
3. Gasoline or 40 120°C C5-C9 As motor fuel, solvent and in dry
petrol or motor (calorific value = 11,250 cleaning.
spirit. kcal/kg)
4. Naphtha or 120 180°C C9-C10 As solvent and in dry cleaning.
solvent spirit.
5. Kerosene oil. 180-250°C C10-C16 As an illuminant, jet engine fuel and
(calorific value = 11,000 for preparing laboratory gas.
kcal/kg)
6. Diesel oil or fuel 250 320°C C10-C18 Diesel engine fuel.
oil or gas oil. (calorific value = 11,000
kcal/kg)
7. Heavy oil. 320-400°C C17-C30 For getting gaso-line by cracking
process.
This on refn
tionation gives:
(a) Lubricating oil. As lubricant.
(b) Petroleum As lubricant and in cosmetics and
jelly. (vaseline) medicines.
(c) Grease. As lubricant.
(d) Paraffin wax. In candles, boot polishes, wax paper,
tarpolin cloth, etc.
8. Residue may be Above 400°C Ca0 and above.
either:
(a) Asphalt. Water-proofing of roofs and rad
or making.
(b) Petroleum coke. moulding arc light
As a fuel and in
rods.
 FUELS AND COMBUSTION 75
Gases

Petroleum
Tray ether
Gasoline
Chimney
Down- Naphtha
spot
Loose Kerosene
cap Fig. 8. Fractional distillation of
Diesel oil crude petroleum.

Lubricating
oil

Steam

Crude
oil Fumace
at 400°C Heavy oil

A brief description of three most important liquid fuels derived from petroleum is given on
below
Easoline or petrol is a obtained between 40-120°Cnd is a mixture of hydrocarbons such as
CHpentane) to CH1s (octane).Its approximate composition is C= 84%; H = 15% ; N+ S+O
= 1%.Its calorific value is about 11,250 kcal/kg. It is highly volatile, inflammable and uesi as fuel for
internal commbustion engines of automobiles and aeroplanes.
Table 5. Comparison of diesel fuel with gasoline fuel.
Diesel fuel Gasoline fuel
Costlier.
is cheaper than gasoline.
ts consumption per unit of power produced is less. | More consumption.
ts thermal efficiency is higher (about 30-35%). Lower thermal efficiency.
s exhaust gases contain lesser amount of Its exhaust gases contain higher amount of
pollutants (CO, oxides of N, hydrocarbon, etc.).pollutant gases.
Its a
cmbustion Tequires complex and more Its combustion requires a rather simpleinternal
combustion engine.
expensive fuel injection device.
ts combustion requires heavy equipment to | No compressed is needed during combustion of
compress air. Lgasoline.
Kerosene oilis a fraction obtained between180-250°C and is a mixture of hydrocarbons such
as Cqofz2 (decane) to Czis4(hexadecane). Its approximate composition is C= 84%, H = 16% ; with
:

lessthan 0.19%S. Iis specific gravity is 0.75-0.85. Its calorific value is 11,100 kcal/kg. Due to high boiling
point range, kerosene does not vaporise easily. It is used as domesticfuel in stoves, as jet engine fuel
and for making oil gas. /o16
Diesel oil is a fraction obtained betrween 250-320C and is a mixture C15Hs to Casas
hydrocarbons. Its density is 0.86 to 0.95. Its calorific value is about 11,000 kcal/kg. Its is used as a diesel
engine fuel.
 ENGINEERING CHEMISTRY
76

s CRACKING
Cracking is defined as "the decomposition of bigger hydrocarbon molecules into simpler,
simnler low
boiling hydrocarbons of lower molecular weight", e.g.,
Cracking
CoHa2 C5H12 + CsH1o
(Decane) (n-pentane) (Pentene)

B. p. = 174 °C B.p. = 36 °C

Of all the fractions obtained by fractionation of petroleum, gasoline has the largest demand
as a motor fuel, but the yield of this fractions is only 20% of the crude. Also the quality of
so-called
'straight-run' gasoline is not high. It has to be properly blended. Moreover,
there is a surplus ofheavier
petroleum fractions. To overcome these difficulties,
the middle and heavy fractions are cracked to
get petrol. The petrol made by cracking has far better characteristics
(as for as the internal com-
bustion engine is concerned) than 'straight-run' petrol. There are two methods of cracking in use:
A hermal cracking :The heavy oils are subjected to high temperatureand pressure, when the
bigge ydrocarbon molecules break dorwn to give smaller mnolecules of the parafins, olefines plus some
hydrogen This process may be carried out either in liquid-phase' or vapour-phase
(a) Liquid-phase thermal cracking: The heavy oil or gas oil stock is cracked
at a suitable
temperature of 475-530°C and under pressure of 100 kg/cm. The cracked products are then
separated in a fractionating column. The yield is 50-60% and octane rating of the petrol produced is
65-70.
(b) Vapour-phase thermal cracking: The cracking oil is first vaporised
and then cracked at
about 600-650°C and under a low pressure of 10-20 kg/cmThis process is suitable only for those
oils, which may be readily vaporized. t requires less time than the liquid-phase method. Petrol
obtained from vapour-phase cracking has better anti-knock properties, but poorer stability than petrol
from liqid-phase cracking,
Catalytic cracking:The quality and yield of gasoline produced by crackingcan be greatln
impoved by using a suitablecatalyst like aluminium silicate, Al,(SiO3 or alumina Al,O,.rt SPa
Advantages: (The yield of petrol is higher,2The quality of petrol produced is better.
INo externl
fuel is necessary for cracking. The heat required for cracking is derived from the coal, embedded in the catalyst.
(4) A much lower pressure (about 1-5 kg/cm) is needed in catalytic cracking.
3 The cracking process can
easily be controlled, so the desired products can be obtaiped. 6) The evolution of by-product gases can be
minimised, thereby the yield of desired petrol is higherThe product of crackingcontains a higher amount
of aromatic and henceit possesses betteranti-knock characteristics. (8) Isomerization to branched-chain com

pounds (iso-paraffins) occur, thereby better petrol is produced.(9) The product contains a very little amount of
undesirable S, because a major portion of it escapes out as H,S gas, during cracking. (10) The percentage of
gum or gum-forming compounds is very low. (11) Catalysts are selective in their action and, therefore, they
permit cracking of only the high-boiling hydrocarbons. (12) n presence of catalyst, cracking iš more of
naphthenic materials than of paraffinic. So the products of catalytic cracking are more paraffinic. (13) Decom-
position of aromatics removes only the side chains, but no ring itself is broken.
There are two methods of catalytic cracking in use
(a) Fixed-bed catalytic cracking : The oil vapours are heated in a pre-heater to cracking
temperatures ( 420-450°C) and then forced through a catalytic chamber (containing artificial clay
mixed with zirconium oxide) maintained at 425-450°C and 1.5 kg/cm pressure. During their
 FUELS AND COMBUSTION
77
passage through the tower, about 40% of the charge is converted
into gasoline and about 2-4%
carbon is formed. The latter gets adsorbed on the catalyst bed.
The vapours produced are then passed
through a fractionating column, where heavy oil fractions
condense. The vapours are then led
through a cooler, where some of the gases are condensed
along-with gasoline and uncondensed
gases move on. The gasoline containing some dissolved
gases is then sent to a 'stabilizer, where the
dissolved gases are removed and pure gasoline is
obtained (see Fig. 9).
The catalyst, after 8 to 10 hours, stops functioning, due to
formed during cracking| This is re-activated by burming off the
carbon,
deposition of black layer of
Te-activation interoal,the vapours'ure dtverted the deposited carbon. Duringthe
throughanother catalyst chamber,
Cracked Cooler
Catalyst vapour Stabilizer
Gases
Heavy Gasoline
oil charge
Fig. 9. 'Fixed-bed catalytic
Haevy cracking.
Pre-heater Catalyst Fractionating
(425-450C) chamber coloumn Gasoline
(425-450t) +
some dissolved gas

(b) Moving-bed catalytic cracking The solid

catalyst is very finely powdered, so that it
behaves almostas a fluid, which can be circulated in
gas stream. The vapours of cracking stock (gas
oil, heavy oil, etc.) mixed with fluidised
catalyst is forced up into a large reactor "bed' in which
cracking of the heavier into lighter molecules occurs (see
Fig. 10). Near the top of the reactor, there
is a centrifugal separator (called cyclone),
which allows only the cracked oil vapours to
thefractionating column, but retains all the catalyst powder in the reactor itself. Thepass on to
catalyst
powder gradually becomes heavier, due to coating with carbon, and
from where it is forced by an air blast to regenerator settles to the bottom,
(maintained at 600°C).

Flue gases Cracked

vapour Light Cooler
fraction
,Cyclone
Gases
Catalyst
regenerator 00 500
Gases
Regenerator Fig. 10. Moving-bed type catalytic
catalyst Stabilizer cracking.
Reactor Heavy
Spent
Feed- catalyst oil Gasoline
oil Air+spent Fraction Gasoline
matching +gas
Catalyst catalyst coloumn
oil -Air

Blower

In regenerator, carbon is
ror mixing with
burnt and the regenerated catalyst then flows through a stand-pipe
fresh batch of incoming cracking oil. At
Separator, which permits only the top of the regenerator, there 1s a
gases (CO, etc.) to pass out, but holds back catalyst particles.
 ENGINEERING
78 CHEMs

20 SYNTHETIC PETROL
Petrol is synthesised by any of the following three methods
Polymerization: The gases obtained as a by-product from cracking of heavy oil
contain olerins(likeethylene, propene
and butenes) and alkanes (such as methane, ethane, propare,
butane). When this gaseous mixture is subjected to high pressure and high temperature, wit
gasol
without the presence of catalyst, it polymerises to form higher hydrocarbons, resembling gasoline,
called polymer gaoline.
Pressure, heat
= CH,= CH.CH,CH,.CH(CH),
HCHPropene) CH, + CH,CHCH =CH, 5-Methyl hexene-1
(Butene-1) and/or catalyst

The pe'ymerization is of fwo types :

Thermal polymerization in which polymerization of cracked gases is carried out at
500-600C and 70-350 kg/m pressure. The product is gasoline and gas oil mixture, which a
separated by fractionation.
( Catalytic polymerization is carried out in presence of catalyst like phosphoricacid. In
this case, lower temperature of 150-200°C is employed. Products are gasoline and unpolymerized
gas. The latter is separated andrecycled for polymerization.
(2) Fischer-Tropsch method: Water gas (CO+H), produced by passing steam over heated
coke, is mixed with hydrogen. The gas is purified by passing through Fe,O, (to remove HS ) and
then into a mixture of Fe,Og. Na,CO, (to remove organic sulphur compounds). The purified gas
is Compressed to 5 to 25 atm and then led through a comvertor (containing a catalyst, consisting of
Catalyst
(Co+Th+Mgo
+Keiselguhr)
Cooler
Fe Fe,Og
+
Na,CO T Gasoline

Water gas
(CO+H) CrackingGasoline
Heavy
oil

Compressor
Purification (5-25 atm) Fractionating
H2 of gas column

Fig. 11. Fisher-Tropsch method.

a mixture of 100 partscobalt, 5 parts thoria, 8 parts magnesia, and 200 parts keiselguhar earth), main
tained at about200-300C.A mixture of saturated and unsaturated hydrocarbons resulis
n CO +2nH2 C,Han + n H,O
CO + (2n+ 1) H2
n C,H2ne2 + H,O n
The reaction isexothermic, so outcoming hot gaseous mixture is led to a cooler, where a liquid
resembling crude oil is obtained. The crude oil thus obtained isthen fractionated to yield: () gasoline
and (fi) high-boiling heavy oil. The heavy oil is reused for cracking to get more gasoline
(3) Rorgius process: The low ash coal isfinely powdered and made into a paste with heavy o
and then a catalyst (composed of tin or nickel oleate) is incorporated. The whole is heated witn
 FUELS AND COMBUSTION 79
hydrogen at 450°C and under a pressure 200-250 atm for about 1.5 hours, during which hydrogen
combines with coal to form saturated hydrocarbons, which decompose at prevailing high temperature and
pressure to yield low-boiling liquid hydrocarbons. The issuing gases (from the reaction vessel) are led
to condenser, where a liquid resembling crude oil is obtained, which is then fractionated to get
() gasoline, (ii) middle oil, and (ii) heavy oil. The latter is used again for making paste with fresh coal
dust. The middle oil is hydrogenated in vapour-phase in presence of a solid catalyst to yields more
gasoline. The yields of gasoline in about 60% of the coal dust used.
Powedered
coal
Heav Catayst Gases Condenser Gases
oil

JEPaste
(Sn or
oleate)
Ni

Gasoline
Ha
Fig. 12. Bergius process of
ioe Gasoline hydrogenation of coal
to gasoline.
Heavy
Loil

Convertor at Crude Fractionating

450C and 200-250 atm oil coloumn
23 KNOCKING
In an internal combustion engine, a mixture of gasoline
the initiation of the combustion reaction, by vapour and air is used as a fuel. After
Smoothly through the gaseous
spark in the cylinder, the flame should spread rapidly and
mixture, thereby the expanding gas drives the piston
cylinder.The ratio of the gaseous volume in the cylinder at the end down the
the end of compression-stroke of the piston, is of the suction-stroke to the volume at
known the 'compression ratio'. The efficiency
internal combustion engine increases with the increase of an
in compression ratio, which is dependent
on the nature of the constitents present in the gasoline used. In
certain circumstances (due to the
presence of some constituents in the gasoline used), the rate of oxidation becomes
so great that the last
portion of the fuel-air mixture gets ignited 1nstantaneously,
an
producing explosive violence, known as
'knocking. The knockingresults in loss ofeficiency.
Chemical structure and knocking: The tendency of fuel constituents to
following order: knock is in the
Straight-chain paraffins > branched-chain paraffins (i.e., iso-paraffins) > olefins > cyclo
paraffins (i.e., naphthalenes) > aromatics.
LThus, olefines of the samme carbon-chain length possess better anti-knock
properties than the corre-
spondingparaffins and so on.
Octane rating (introduced by Edger in 1872) : It has been found that n-heptane knocks very
badly and hence, its anti-knock value has arbitrarily
been given zero. On the other hand, isooctane
(2:2:4-trimethyl pentane),
HHH HHHH H CH3 HH
CH H
H-C-C-C-C-C-C-C-H H-C-C -C-H
HHH HH H H H CH H H H
(Octane No. = 0) (Octane No. = 100)
 ENGINEERING CHEMISTRY
82 (o
Thus, octane number
knocking, so its anti-knock value has been given as'100.
combustion engine fue) s the percentage of isooctane a
gives very little in
of
rating) a gasoline (or any other internal
mnatches the fuel under test in knocking characteristics. In this
mixture of is00Ctane and n-heptane, which
characteristics as a 80:20 mixture
way, a80-octanefuel is one which has the same combustion
of isooctane and
n-heptane.
Improvementof anti-knock.characteristics of a fuel : The octane number of
I.C. fuels can

be raised by the addition of such

extremely poisonous materials as tetra ethyl Tead, (CH5,Pb or TEL
mL and in aviation fuels, about
and diethyl telluride, (C2H5),Te. In motor spirit (or motor fuel), about 0.5
per
1.0to 1.5 mL of TEL 1S added Iitre of petrol.
finely divided lead oxide
According to the most accepted theory, TEL is converted into a cloud of
molecules formed, thereby
particles in the cylinder and these particles react with any hydrocarbon peroxide
chances of any early detonation.
slowing down the chain oxidation reaction and thus, decreasing the
in order to help the
However, deposit of lead oxide is harmful to the engine life. Consequently,
amount of ethylene dibro-
Simultaneouselimination of lead oxide formed from the engine, a small
volatile lead bromide along-
mide is also added to petrol. Ethylene dibromide removes lead oxide as
reduces the effectiveness of the TEL
With the exhaust gases. The presence of sulphur compounds in petrol
Pb +CH,Br - CH,Br PbBr +CH=CH
Ethylene dibromide Lead bromide Ethylene
tetra ethyl
Unleaded petrol: Octane rating of petrol is in leaded petrol is increased by adding
lead or tetramethyl lead. However, combustion of lead petrol leads to formation of litharge
(PbO),
which deposition the inner wall of cylinder and jams the piston. Also leaded petrol cannot be used
in automobiles equipped cost catalytic converter, because lead present in exhaust gas poisons the
catalyst, thereby destroying the active sites. Alternative method of increasing octane number of
petrol is to add nigh octane compounds like isopentane, isooctane, ethyl bernzene, isopropyl benzene, methy
iertiary butyl ether (MTBE). Out of these MTBE is preferred, because it contains oxygen in the form
of ether group and supplies oxiygen for the combustion of petrol in internal combustion engines, thereby
reducingthe extentof peroxy compound formation. "Unleaded petrol" is one where in the enhancement
of octane rating is accomplished without the addition of lead compounds.
It may be pointed here that a major advantage of unleaded petrol is that it permits the use of
catalytic converter attached to the exhaust in automobiles. A catalytic converter contains a catalyst
(rhodium), which converts the toxic gases (CO and NO) to harmless gases (CO, and N, respectively).
Moreover, it oxidises unburnt hydrocarbon into CO, and H,O.
DIESEL ENGINE FUELS
In a diesel engine, the fuel is exploded not by a spark, but by the application ofheat and pressure.
Diesel engine fuels consist of longer chain hydrocarbons than internal combustion engine fuels. The main
characteristic of diesel engine fuel is that it should easily ignite below compression temperature, and
there should be as short an induction lag as possible. This means that it is essential that the hydrocarbon
molecules in a diesel fuel should beas for as possible the "straight-chain" ones, with a minimum admixture
of aromatic and side-chain hydrocarbon molecules.
The suitability of a diesel fuel is determined by its centane value, which is the percentage of
hexadecane in a mixture of hexadecane and 2-methyl naphthalene, which has the same ignition character
istics as the diesel fuel in question. The cetane number ofa diesel fuel can be raised by the addition
of small quantity of certain "pre-ignition dopes" like ethyl nitrite, isoamyl nitrite, acetone peroxide,
etc.
FUELS AND COMBUSTION
83
H HH H
C-H H-C-C-C-H
H H
2 Methyl naphthalene
(Cetane No. = 0)
n-Hexadecane
(Cetane No. = 100)
The usual diesel engine fuel is diesel oil or gas oil, a fraction obtained
between 250-320°C
during the fractional distillation of crude petroleum. This oil, generally,
contains 85% C and 12%
H. Its calorific value is about 11,000 kcal/kg. Ignition quality order among hydrocarbon
constituents
of a diesel fuel is as follows:
n-alkanes > naphthalenes > alkenes > branched alkanes > aromatics.
Thus, hydrocarbons which are poor gasoline fuels are quite good diesel fuels.
High-speed and low-speed diesels: In a high-speed diesel engine, the time lag in getting
the diesel droplets heated to ignition point is very brief, about 1/500th of a second. Such diesel
engines require diesel with cetane numbers in excess of 45 (upto 60). On the other hand, low speed
diesel requires cetane number of about 25. Cetane number of medium speed diesel is about 35.